Shrink resistant impregnated wool



United States Patent 3,427,193 SHRINK RESISTANT IMPREGNATED WOOL Walter R. Wszolek, Sykesville, Md., assignor to W. R. Grace & Co., New York, N.Y., a corporation of Connecticut No Drawing. Continuation-impart of application Ser. No. 450,499, Apr. 23, 1965. This application July 26, 1967, Ser. No. 656,066 US. Cl. 117-141 Int. Cl. D06c 29/00 Claims ABSTRACT OF THE DISCLOSURE This application is a continuatiou-in-part of application having Ser. No. 450,499 filed Apr. 23, 1965, now abandoned, which in turn is a continuation-in-part of application having Ser. No. 394,331 filed Sept. 3, 1964, now Patent No. 3,343,983 which in turn is a continuation-inpart of application having Ser. No. 343,915 filed Feb. 6, 1964, now abandoned, which in turn is a continuation-inpart of application having Ser. No. 337,742 filed Jan. 15, 1964, now abandoned.

Keratinous fibers such as Wool tend to shrink and/or felt during Washing thereby destroying to a large extent their commercial value. In a description of this invention the term felt refers to that property of such fibers which causes them to close upon each other in washing, or other treatment in aqueous or other liquor in which the Wool material is repeatedly squeezed and rubbed, so that the material becomes denser and more compact. This property of felting is primarily responsible for shrinkage which woolen yarns and fabrics suffer when washed. Thus a commercially acceptable method of shrinkproofing wool without adversely effecting other inherent desirable properties of the material has been a long felt want.

The use of emulsions of ethylene homopolymers for improving the tear strength and the hand of resin treated fabrics in the textile industry is known. See US. 2,928,- 816 and US. 2,766,214. However, these polyethylene emulsions because of their low molecular weight, i.e., an RSV less than 0.1 do not afford shrinkproofing when applied to wool. In a copending application having Ser. No. 394,331 filed Sept. 3, 1964 a method is taught whereby shrinkproofing of wool is accomplished with emulsions of polyethylene in combination with a crosslinking agent. The resultant crosslinked polymer is of sutficiently high molecular weight to afiord shrinkproofing to wool However, this latter system has the drawback that on the application of acid dye to the shrinkproofed wool, the crosslinks break down and the shrinkproofing effect is destroyed. Since acid dyes are the most commercially ac- "ice ceptable dyes used in the art due to their brightness and fastness and since the dyeing operation for commercial reasons is usually performed subsequent to the crosslinking step, it is advantageous to find a method of shrinkproofing wool which would be practical under normal methods of forming a finished woolen product.

One object of the instant invention is to shrinkproof wool. Still another object of the instant invention is to shrinkproof wool which will not be affected by subsequent dying operations on the wool. Yet another object of the instant invention is to shrinkproof wool without substantially altering its hand. These and other objects of the invention will be apparent from a reading, hereinafter.

These objects are accomplished by the present invention by impregnating textile fibers, e.g., wool and .wool blends with an aqueous emulsion of a member of the group consisting of ethylene homopolymer and copolymers of ethylene wherein said copolymer contains at least mole percent ethylene, said group members having a reduced specific viscosity of at least 0.5 deciliter/g. and thereafter removing the liquid therefrom.

The invention further provides a composition consisting essentially of a textile fiber impregnated with l to 25 percent by weight based on the total weight of the impregnated fiber of an aqueous emulsion of a member of the group consisting of ethylene homopolymer and copolymers of ethylene wherein said copolymer contains at least 50 mole percent ethylene and said group members have a reduced specific viscosity of at least 0.5 deciliter/ g.

The group members operable in emulsion form herein include ethylene homopolymer and ethylene copolymers containing at least 50 mole percent ethylene wherein said homopolymer and copolymers have a reduced specific viscosity of at least 0.5 deciliter/g. Thus examples of ethylene homopolymer operable in the instant invention include an oxidized polyethylene having a density of 098 and RSV of 0.77 and containing 0.58 milliequivalent carbonyl and 0.35 milliequivalent carboxyl per gram polymer made from an ethylene polymer of high molecular weight sold under the trade name Hifax 1900 by Hercules Corporation. Another ethylene homopolymer operable in the instant invention is an emulsion polymerized ethylene homopolymer having a reduced specific viscosity of 0.77 sold under the trade name Poly BM 40 by Spencer Chemical Division. Examples of copolymers of ethylene operable in the instant invention include an aqueous emulsion of a copolymer of ethylene and methacryclic acid where a portion of the m-ethacrylic acid is present as a sodium salt in order to help stabilize the aqueous emulsion. The copolymer contains at least 50 mole percent ethylene, 0.1 to 3.0 milliequivalents carboxyl per gram copolymer and has a reduced specific viscosity in excess of 0.5. This copolymer is sold under the trade name Surlyn D 1000 series by E. I. du Pont de Nemours & Co. In another commercially available variation of Surlyn D, the copolymer contains in its structure a minor amount of vinyl acetate in addition to the ethylene, methacrylic acid and the sodium salt of methacrylic acid. Other variations in copolymer structure are also possible, including the use of other carboxyl-containing copolymers beside methacrylic acid, other vinyl monomers beside vinyl acetate and other salt-forming basic materials besides sodium hydroxide.

Another example of an emulsifiable copolymer wherein said copolymer contains at least 50 mole percent ethylene is Poly EM 500 series sold as an aqueous emulsion by Spencer Chemical Co. Unlike conventional polymer emulsions, Poly EM 500 series contains no free emulsifying agent. Chemically the polymer is mainly polyethylene (CH CH units with attached carboxylate groups in the form of their alkyl metal salts and amides:

in which .water forms the continuous phase, regardless of the presence or absence of any emulsifying agent.

As used herein the term shrinkprooffing means that the treated garment has less than a area shrinkage subsequent to 10 washings which is commercially acceptable.

The invention is particularly suitable for shrinkproofing wool and blends containing at least 50% wool by weight GOONa CONH:

The polymeric chain is branched with values of w, x, y and z generally much greater than 1. It is also possible to have small amounts of other carboxylate groups present such as free carboxyl (COOH), methyl ester (COOCH or similar related structures. However, the main carboxylate groups present as stated above are the sodium salt (COONa) and the amide (-CONH Still another example of an operable emulsifia-ble ethylene containing copolymer is a modified ethylene acrylic acid copolymer in which the acids have been converted to the amide sold as an aqueous dispersion by the Isochem Corporation under the trade name of Isorez PE 50 which copolymer contains at least 50 mole percent ethylene, and has a reduced specific viscosity in excess of 0.5 deciliter/g.

One advantage of the instant invention is the application of the polymeric material in an aqueous emulsion. It

' is Well known in the shrinkproofing art that various polymers may be applied to wool substrates from various organic solvents, especially the classes of hydrocarbons and chlorinated hydrocarbons such as perchloroethylene. However, the use of such solvents is to be avoided Whereever possible, because of the numerous disadvantages, dangers and excessive cost associated with their use. In the first place, most polymers are not very soluble in organic solvents so that the concentrations which can be achieved are severely limited. In order to achieve concentrations of even 10 to the solvents must be kept hot, causing solvent lost, emanation of obnoxious vapors, fire and explosive hazards and the danger of precipitation and clogging of machinery in the event the temperature of the solvent is allowed to drop.

In addition, solvent systems have the disadvantage that they are corrosive towards machinery causing leaching of lubricants, dissolving of rubber gaskets, hoses, padder rolls and other mechanical problems. Moreover, solvents are so expensive that some type of solvent recovery system is needed. This adds the cost of condensation units, exhaust fans, etc., and such recovery systems have generally been found to perform unsatisfactorily in open areas such as textile mills.

By contrast, aqueous emulsions and suspension can be prepared with a content as high as 40 or 50% at ambient temperature, and are no more hazardous or unpleasant than ordinary soap preparations. They do not tend to corrode or dissolve mechanical parts and if they lose strength through evaporation of water, the water vapor is harmless and the emulsion can be reconstituted by the addition of more water. Since water is the only volatile system, no recovery unit is is required. Aqueous emulsions are non-inflammable and do not present any explosion hazard. There are no poisonous fumes associated with aqueous emulsions, and occasional contact with the skin of operators would not cause health problems. Any spilled material can be easily washed away with water as would be done with soap or floor wax.

It may be seen from the foregoing that aqueous emulsions present very few problems during storage, handling and application to textiles, in contrast to the systems based on organic solvents which are dangerous and expensive.

As used in the present invention, unless Otherwise specified, the term emulsion means a polymer dispersion COONa CONH2 with other natural or synthetic fibers such as polycarbonamides wherein the carbon amide linkage is an integral part of the main polymer chain such as conventional nylon, i.e. 66-nylon poly (hexamethyleneadipamide) or 6-nylon, i.e. poly (ca-prioamide) and the like.

In using a high molecular weight ethylene homopolymer it is necessary to oxidize same to form carboxyl groups on the polymer chain in order to impart emulsifiability to the polymer. Polyethylene can be readily oxidized by various well known methods to give polymers containing carboxyl groups. The technique for introducing carboxyl groups into polyethylene are exemplified by, but are not limited to, the following methods. For example, polyethylene can be milled in ozone and/or air at a temperature in the range 70-200 C. Another method would include passing ozone and/or air into an oven over a solid polyethylene therein at a temperature below the melting point of the polymer, e.g. about 70-135 C. Still another method would be to suspend particles of polyethylene in water or in organic solvent and either bubble air through the suspension or pressurize the system with air at 70-200 C. Yet another method would be to pass ozone and/or air at a temperature below the melting point of the polymers through a fluidized bed of polyethylene particles, A further method would include pressing the polyethylene into film and passing hot air at a temperature at 70200 C. thereover. In all the aforestated methods of oxidizing polyethylene, if desired, a minor amount, i.e. 0.05 to 5% by weight of an organic peroxide, nitrogen tetroxide or other oxidation catalyst may be blended with the polymer to increase the oxidation rate. An additional method of preparing polyethylene for the instant invention is by an emulsion polymerization process wherein the ethylene monomer is polymerized at temperatures of l40 C. in aqueous media in combination with an alcohol in the presence of emulsifying agents and a free radical catalyst such as potassium persulfate.

The general procedure of performing the present invention is to oxidize the polyethylene by one of the aforementioned methods, e.g. admix the polyethylene preferably in particulate solid form, with an organic peroxide (usually 0.1 to 5% peroxide by weight of polymer) in a suitable mixing mechanism, e.g. Twin Shell blender at room temperature. Preferably the organic peroxide is solubilized in a hydrocarbon solvent which solvent is thereafter evaporated prior to the oxidation step. Solubilizing the peroxide in a solvent insures more uniform dispersion of the peroxide throughout the polymer. Various solvents for the peroxide are operable and the selection of a suitable one is governed by its solvent power on the peroxide employed and its inertness thereto. Operable solvents include volatile aromatic and aliphatic hydrocarbons such as benzene, toluene, pentane, hexane and the like.

The thus blended polymer-peroxide mixture is then subjected to oxidation until the required amount of carboxyl is present. The amount of carboxyl necessary to afford emulsifiability to the ethylene homopolymer is usually within the range 0.1 to 3.0 milliequivalents carboxyl per gram of polymer.

In the case of ethylene-containing copolymers wherein the comonomer contains hydroxyl groups the oxidation step is obviously not necessary. The oxidized polyethylene or carboxyl containing ethylene copolymer of the instant invention is readily emulsified in a continuous aqueous phase in the presence of suitable emulsifiers and sufiicient base to neutralize the carboxylic acid groups present in the polymer. Both ionic and non-ionic emulsifying agents well known in the prior art are operable to emulsify. the polymer. Ionic emulsifiers include, in the anionic class, amine salts of fatty acids. Morpholine, mono-ethanol amine, Z-amino-Z-methyl-l-propanol are suitable amines. Operable fatty acids include oleic, stearic, palmitic, myristie and the like higher fatty acids. Sodium, potassium and ammonium salts of the fatty acids are also operable. Salts of alkyl aryl sulfonic acids have also been used as emulsifying agents with good results. Operable ionic emulsifiers in the cationic class include, but are not limited to, acetate salts of long chain aliphatic amines. Polyoxyethylene esters of fatty acids, polyoxyethylene derivatives of sorbitans or of fatty acid substituted sorbitans, polyoxyethylene ethers of long chain alcohols, polyoxyethylene ethers of alkyl aryl phenols or combinations thereof are examples of a few non-ionic emulsifiers operable in this invention.

The amount of base added to the emulsion ranges from 40% to 200% of the theoretical amount required to neutralize the acid groups on the polymer. When anionic emulsifiers such as amine salts of fatty acids are used, one generally adds an excess of the amine moiety to serve as the base.

The water: polymer ratio in the prepared emulsion is in the range 80 to 2:000: 100 parts by weight, preferably 150 to 1000: 100 parts by weight respectively and can subsequently be diluted or concentrated as desired for any particular end use.

After oxidation, if necessary, the oxidized polymer or carboxyl-containing ethylene copolymer, emulsifier, base, and water are combined in any order in a pressure reactor equipped with an efficient stirrer. The reactor is sealed and the mixture is heated with vigorous stirring to a temperature ranging from the melting point of the polymer up to 200 C. or more (preferably 1l0-160 C.) and maintained thereat for periods ranging from 5 minutes to 6 hours under the pressure of the system.

For treating the textile fabrics in accord with the instant invention the polymer material in emulsion form can be added to the fabric in several ways. For example, the polymer in emulsion form can be sprayed or brushed on the fabric. Another method would be to immerse the fabric in the emulsion of the polymer. Excess liquid can then be removed by heat, evaporation, passage of the impregnated fabric through squeeze rolls, any combination thereof or other well known means. To obtain the shrinkproofing benefits of the instant invention it is necessaiy that the fabric be impregnated with 1 to 25%, preferably 210%, by weight of the polymer based on the total weight of the impregnated fabric. Lesser amounts do not afford sufficient shrinkproofing whereas amounts in excess of the upper limit, although operable, impart a weight percent add-on in excess of that desired for ordinary commercial use of wool. However, in special instances, e.g. if unusual fabric performance (abrasion resistance, solvent or corrosion resistance, etc.) rather than low cost is the overriding consideration, the upper limit may be traversed.

In most of the examples herein, unless otherwise noted,

standard wool swatches 5" x 5", marked with ink to form 4% x 4%" squares to facilitate measurements were weighed and immersed in the emulsion until uniformly wetted. The wetted swatches were squeezed through rubber rolls to remove excess emulsion. The thus impregnated swatches were dried by bolting same in a wooden frame without stretching and placing the framed swatches in a forced air oven. The swatches were weighed after drying to determine the percent add-on. The area inside the mark area on the swatches was measured and designated as the initial area. The swatches were then washed individually in a one quart friction lid paint can with 6 #00 rubber stoppers and 100 ml. soap solution containing 0.2% soap flakes and 0.1% sodium carbonate by weight in distilled water at 50 C. The can was agitated for 15 minutes on a paint can shaker. The swatch was removed from the can, rinsed in warm water and air dried. The dried swatch was then measured for surface area inside the marked portion to obtain percent shrinkage in area. The swatch was then recharged to the container along with another new charge of soap solution for a second 15 minute wash at 50 C. The procedure was repeated a third time in some cases. The swatch is again rinsed, air dried and measured. The percent area of shrinkage is equal to area after washing 100 initial area In other tests the laundering of the wool swatches (in this case 12" x 12"), after relaxing the swatches in 0.1% non-ionic wetting agent for 1 hour, drying and marking with 10" x 10" squares, was done in an automatic washing machine (delicate fabric setting) having a 4 minute sudsing cycle and a 13 minute rinsing and spin drying cycle. 30 gms. of deter-gent sold under the trade name Tide by Procter & Gamble Co. was used per wash. The temperature of the wash water (warm setting) was 96 F. After washing, the swatches were dried in a gas dryer (hot setting) for about 18 minutes at about 185 F. The washing and drying cycle was repeated 10 times with the area of the swatches being measured after the first, fifth and tenth cycle to obtain the percent area of shrinkage.

Various techniques are operable to perform the consolidation of the polymer on the treated fabric. For example, the treated material can be passed over one or several internally heated rotary drums, through an infrared drier or through a tenter frame drier. Preferably a tenter frame drier capable of drying the fabric while holding same in a relaxed or in a stretched condition, as desired, is employed. In commercial practice using the tenter frame technique, the treated fabric is maintained in a relaxed or stretched condition in the longitudinal machine direction by the take up roll and in the transverse direction, i.e. in a direction transverse to the machine direction in which the fabric is ultimately wound, by a tenter frame. In the examples herein, wherein swatches of treated fabric are used, the treated fabric was generally clamped between picture-type frames.

The following examples are set down to illustrate the invention and are not deemed to limit its scope.

The extent of oxidation of polyethylene was determined by ascertaining the carboxyl content of the polymeric material by titration with a base in the following manner. About 1 g. of the polymer to be analyzed was accurately weighed and dissolved in 100 ml. of xylene by heating to -130 C. with stirring in a 500 ml. Erlenmyere flask on a magnetic stirrer-hot plate. While continuing stirring and maintaining the temperature at 120- C., the solution was titrated to a pink end point with standard 005 N potassium hydroxide in 30:70 ethanol: xylene using phenol-phth-alein as indicator.

Calculation:

milliequivs. COOH per g.=

(ml. of KOH) (Normality of KOH) g. of polymer 7 i.e. HLMI). Densities of the polymer were measured under the conditions specified in ASTM D 15 -57T.

Reduced specific viscosity, i.e. RSV in units of deciliters/ g. was obtained by dissolving 0.1 g. of the polymer in 100 cc. Decalin at 135 C. in accord with the procedure of ASTM D 1601-61.

Unless otherwise noted all parts and percentages are by weight.

The ratings for hand were made subjectly, excellent meaning a hand as good as the wool had prior to treatment with ratings of very good, good and acceptable of less hand respectively and a rating of unacceptable being the coarsest, stiffest hand.

Example I 100 parts of oxidized polyethylene having a density of 0.98, and RSV of 0.77 and containing 0.58 milliequivalent carbonyl and 0.35 milliequivalent carboxyl/ g. polymer were charged to a Chemco reactor equipped with an air stirrer along with 31 parts of a non-ionic emulsifier, i.e. Renex 697, 5.5 parts of a 32% KOH solution and 450 parts water. The reactor was sealed, stirring commenced and the reactor was heated to 150 C. After 30 minutes at 150 C. and 7072 p.s.i.g., the reactor was cooled with continued stirring. The resultant non-ionic polyethylene emulsion contained 22.4% solids, has a viscosity of 7 centipoises and a pH of 10.2. A portion of the thus formed emulsion was poured into a shallow glass baking dish. A preweighed wool swatch, (i.e. J. P. Stevens all wool fabric 513200) of 12" x 12 dimension was dipped in the emulsion, nipped through squeezed rolls to a total solids add-on of 13.5% and thereafter dried for minutes at 150 C. The swatch was then prescoured in a water bath at room temperature for 20 minutes in a stainless steel tank to remove excess emulsifier. Ammonium sulfate, and a detergent, i.e. Irgasol DA manufactured by Geigy Chemical Co., both in an amount equal to 2% of the weight of the wool prior to treatment was added to the bath and the bath temperature was raised from 70 F. to 120 F. The swatch remained in the bath for a period of 20 minutes. Thereafter neutral premetallized green dye, i.e. Cibalan Green DL manufactured by Ciba Inc. was dissolved in a small amount of water and added to the bath in an amount equal to 1% by weight of the untreated wool. The dye was added to the bath over a minute period at 120 F. After the addition of all the dye, the bath was brought to a boil over a 30 minute period. The swatch was left in the boiling bath for 45 minutes. The swatch was then removed from the bath, rinsed at 120 F. for 10 minutes followed by a 5 minute cold rinse and dried. A square area of approximately 10" on a side was accurately measured and marked on the swatch. This measurement is called the original measurement (OM). The swatch was then relaxed by soaking for 1 hour in a 0.1 weight percent aqueous solution of a polyoxyethylene nonylphenol ether sold under the trade name Renex 697. After the relaxation treatment the swatch was again accurately measured for a 10" square. This measurement is called the relaxation measurement (RM).

The swatch was then washed according to the following procedure. The relaxed swatch to be tested and such additional ballast as was necessary to make up a 3 lb. load was placed in a washer. Sufficient water at 100 F. to give a 7" water level for the sudsing operation was added to the washer. 30 ml. of a 30% by weight solution of polyphosphate, 170 grams of borax, and sufficient neutral soap so that a 1" head of suds is produced and maintained during the entire wash was added to the washer. The wash cycle consisted of a 75-minute wash at a 7" water level at 100 F., followed by a 10 minute first rinse at a 7" water level at 100 F. which in turn was followed by a 5 minute second rinse at a 7" water level at a 100 F. for a total 90 minute cycle. Thereafter the swatch was removed and dried as follows. The swatch was placed in a flat bed press and air dried at a temperature of 275300 F. After drying the swatch was laid on a flat surface without tension, wrinkles or creases and conditioned for at least 4 hours. The swatch was again accurately measured for a 10" square and marked.

Calculations for measuring shrinkage were made as follows:

O.M. minus R.M.

Percent relaxation shrinkage OIM. X 100 Percent total shrinkage= a i X 100 Percent felting shrinkage=percent total shrinkage minus percent relaxation shrinkage here:

O.M.=original measurement R.M.=relaxation measurement W.M.=measurement after washing and drying cycle The emulsion treated, dyed wool swatch had a felting shrinkage of 1.5% and a total shrinkage of 4.5%.

Example 2 Example 3 The procedure of Example 1 was repeated except that the emulsion used was Surlyn D 1000 series, produced by E. I. du Pont de Nemours & Co. instead of the oxidized polyethylene emulsion. Surlyn D is an aqueous emulsion of a copolymer of ethylene and methacrylic acid wherein a portion of the methacrylic acid is present as the sodium salt and the copolymer contains at least 50 mole percent ethylene, 0.1 to 3.0 milliequivalents carboxyl/g. copolymer and has an RSV greater than 0.5 deciliter/ g. The wool swatch after treatment as in Example 1 in the neutral dye, i.e. Cibalan Green DL had a felting shrinkage of 4.0% and a total shrinkage of 7 .0%.

Example 4 Example 3 was repeated except that the acid dye, i.e. Neolan Bordeaux Red RM, was substituted for the neutral dye, Cibalan Green DL, and the bath was maintained at a pH in the range 2-3 by addition of H The thus treated wool swatch had a felting shrinkage of 5.0% and a total shrinkage of 6.0%

Thus it can be seen that by practice of this invention as shown by Examples 1-4, it is possible to dye, even acid dye, the emulsion treated wool subsequent to said treatment. In all the above cases the dye was true and fast and the handle of the washed emulsion-treated, dyed fabric was as good as, if not superior to, the original untreated wool fabric.

The following examples show the operability and inoperability of various polymers in the instant invention.

Example 5 250 lbs. of commercially available polyethylene having a density of 0.95, a melting point of '135 C., a reduced viscosity of 4.5 and a high load melt index of 1.4 was oxidized in air in a ribbon blender for 57 hours at a temperature of 114-118 C. The thus oxidized polyethylene on characterization had a density of 0.99, a melt index of 540, a reduced specific viscosity of 0.48 deciliter/g, and contained 0.50 milliequivalent of carboxyl/ g. of polymer and 0.79 milliequivalent of carbonyl/g. polymer.

9 Example 6 10,000 g. of the thus oxidized polyethylene from Example along with 1800 g. oleic acid, 1750 g. morpholine and 45,000 g. of distilled water were charged to a Patterson Kelly 25 gallon kettle equipped with an air stirred (640 r.p.m.). The kettle was sealed and vigorous stirring was commenced while the kettle reactor was heated to 150 C. The reactants were maintained at 149- 152 C. and about 60 p.s.i.g. for 30 minutes with vigorous stirring. Stirring was continued while the thus formed emulsion was cooled to room temperature. The resulting anionic type emulsion contained 21% solids, had a viscosity of 7.8 centipoises at 23 C. and a pH of 9.1.

Example 7 400 ml. of the thus formed emulsion from Example 6 were poured into a shallow glass baking dish. A wool swatch 5" x 5", with a 4% x 4%" square marked thereon to facilitate measurement, was immersed in the emulsion at room temperature, i.e. 25 C. The swatch was then wrung through a set of rubber squeeze rolls to remove excess emulsion from the swatch. The dipping and wringing operation was repeated one more time. The wool swatch was then clamped between two picture ty-pe frames which has 4 /2" squares cut from their centers. The treated swatch clamped in the frame was inserted into a forced air oven preset at 150 C. and remained therein for minutes to bake the emulsion onto the swatch. The dried swatch was then removed from the frames and weighed. The difference in weight between the treated swatch and the untreated swatch is referred to herein as the weight percent add on and was 7.8%. The area of the swatch within the markings was remeasured and designated as the initial area. The swatch was then washed individually in a one quart friction lid paint can containing 100 ml. of soap solution and 6 #00 rubber stoppers. The soap solution contained 0.2% Ivory soap and 0.1% Na CO in distilled water. The soap solution was heated to 50 C. at the start of the wash cycle. The can was agitated for minutes on a paint can shaker. The sample swatch was removed from the can, rinsed several times with warm water and then hung to dry. After 10 washings and dryings the swatch had a percent area shrinkage of 16.8. A control sample of the same fabric which had not been subjected to the oxidized polyethylene emulsion bat-h showed an area shrinkage of after the 10th wash.

Example 8 Example 7 was repeated except that 1.5 milliequivalents hydrazine per milliequivalent of carbonyl on the polymer was added to the polymer emulsion to crosslink the polymer before the swatch was dipped therein. The resultant crosslinked polymer had an RSV in excess of 0.5 deciliter/ g. The percent area shrinkage after the 10th wash was 6.5%.

Example 7 shows the inoperability of low molecular weight polymer, i.e. polymers having an RSV less than 0.5 deciliter/ g. to afford shrinkproofing to wool. When the polymer is crosslinked as set out in Example 8, i.e. the molecular weight is increased, shrinkproofing of the wool is realized.

The following examples show the effects of dyeing the wool fabric in combination with the shrinkproofing procedure of the instant invention.

Example 9 Preweighed wool swatches (12" x 12") consisting of I. P. Stevens all wool fabric 813200 were used in all the runs in this example.

Three different emulsions were' employed for shrinkproofing and were made up as follows:

Emulsion A.100 parts of commercially available oxidized polyethylene having a density of 0.99, an RSV of 0.33 and containing 0.48 milliequivalent carboxyl and 0.97 milliequivalent carbonyl/ g. of polymer were charged to a Patterson Kelly 25 gallon kettle along with 15.5 parts of a non-ionic emulsifier, i.e. Renex 697, 15.5 parts of Triton X 100, an emulsifier manufactured by Rohm and Haas, 7.2 parts of a 32% KOH solution and 242 parts water. The kettle was sealed and stirring commenced while the kettle was heated to 150 C. After 30 minutes at 150 C. and 55 p.s.i.g., the kettle was cooled with continued stirring. The resultant emulsion contained 34.3% solids. The emulsion had a viscosity of 680 centipoises and a pH of 9.1. 3.0 milliequivalents hydrazine/ g. carbonyl in the polymer was added to the emulsion with stirring to crosslink the polymer. The crosslinked polymer had a RSV in excess of 0.5 deciliter/ g. The emulsion was thereafter diluted with water to obtain the desired percent total solids add-on.

Emulsion B.-Emulsion B is the same emulsion used in Example 1.

Emulsion C.-An aqueous dispersion of Surlyn D" 1000 series available from E. I. du Pont de Nemours & Co. containing 40.9% solids and diluted to 12.3% solids. This is the same emulsion used in Example 3.

The wool swatches were treated with the polymer emulsions by the following procedure. The weighed wool swatches were dipped in the emulsion and nipped through squeezed rolls to the desired add-on. After treatment with Emulsion A, the swatches were cured in an Andrews and Goodrich roller dryer at 300 F. by passing the pieces through twice for a total curing time of 11% minutes.

After treatment with Emulsions B and C, the swatches were dried in a pin tenter frame at 150 C. for 10 minutes.

The Wool swatches were dyed after treatment with the emulsion with both an acid dye, i.e. Neolan Bordeaux Red RM and with a neutral dye, i.e. Cibalan Green DL.

The following procedure was employed when Neolan Bordeaux Red RM was used as the dye.

The acid dyeing of the wool swatches consisted of prescouring the swatches in a water bath for 15 minutes at F. in a stainless steel tank. The tank was then drained and then refilled with fresh water. The temperature of the water bath was raised to 150 F. and 10% sodium sulfate and 20% Neolan Bordeaux Red RM, said percentages being based on the weight of the wool swatches were added to the tank and the swatches were allowed to stand therein for 15 minutes. Thereafter 10% sulfuric acid was added to the bath (pH 2.0) and the bath was raised to a boil over a 30 minute period. The swatches were allowed to remain in the boiling bath for 1% hours. There-after the swatches were rinsed at F. for 10 minutes followed by a 100 F. rinse for 7 minutes and thereafter followed by a cold rinse at 70 F. for 4 minutes. The swatches were padded to remove excess water and dried on a pin tenter frame.

The following procedure was used to dye the wool swatches with Cibalan Green DL after treatment with the polymer emulsion.

A separate dyeing bath was set up in a stainless steel tank consisting of adding swatches to a water bath for 15 minutes at 100 F. and thereafter draining said bath. The bath was refilled with water and the temperature increased to 120 F. Thereafter 2% Irgasol DA, 2% ammonium sulfate, and 1% Cibalan Green DL, said percentages being based on the weight of the untreated wool were added to the bath and the bath temperature was slowly raised to a boil. The swatches were then rinsed at 120 F. for 10 minutes followed by a cold rinse (70 F.) for 5 minutes.

After treatment with emulsion and dyeing the dried swatches were marked and washed in accordance with the procedure of Example 1 herein. After washing the swatches were air dry and hand steamed ironed prior to remeasurement to calculate percent area shrinkage. The percent area shrinkage results after the various procedures employed are given in Table I.

TABLE I Example Polymer Percent Percent area shrinkage o. emulsion total solids Dyeing treatment add-on Felting Total None 21.0 32.5 11.2 do 3.5 5.5 12.6 do 6.0 7.0 12.3 d 3.0 3.5 0 Cibalan Green DL.- 19. 20. 0 11.2 ....-do 7.0 9.0 22.4 --.-.do 1.5 4.5 12.3 do 4.0 7.0 0 Neolan Bordeaux Red R 25. 5 26. 5 11.2 do 14.5 14.5 22.4 6.5 7.0 12.3 5.0 6.0

As can be seen in Table I, the crosslinked polyethylene Example '11 emulsion (having an R SV greater than 0.5 deciliter/g. is Example 10 was repeated except that Isorez PE a operable to afford shrmllgproofing n a nell'tral dye commercially available ethylene-modified acrylic acid coused See Example However Shown m Example polymer described herein was substituted for the Poly 910, subsequent dyeing with an acid dye, breaks down 500 series polymer The Percent area shrinkage was the crosslink-s in the polymer with the resulting low 1110- less than 6%. leculatr g 2 i ig a i fif The process of the invention is particularly adapted to l l l e przvizi s xain i l s isc sail? for th gur pos e of the ltreatrlllwm of T 3 i f i f i fii' ble to ot er texti es inc u ing mo airs; amma an; S1 illustrat on and are not l1m1ted in respect to the method fibers made f proteins sugh as esin, eanut protein, 3 2 22222; gygg 3 fg i gi gz fgy i g gg 25 soybean protein, keratins, etc.; cotton; regenerated cellulose; v1scose; linen; cellulose acetate, etc. The textile dltlonscan'be employed equally as Wen material may be in the form of fibers, threads, yarns,

' E 1 10 woven or knitted fabrics, garments, etc.

Xamp e What is claimed is: I H 1. A shrink resistant impregnated textile article of sub- 1 2013 2 1 z il l v v iglft gerci r it az i i s ol gt i gi i g st-antially unimpaired hand consisting essentially of wool polyoxyethylene nonylphenol ether sold under the trade regnated i 145% by welght basedl on the i name Renex 69-7. The swatch was rinsed and dried Welght of E lmpregnated Wool of a PO ymer of e without tension weighed and a X Square was group conslstmg of ethylene homopolymer and c0 polymarked thereoli. The swatch was then dipped at room mars of ethylene Wherem sald.copolymers temperature (25 C.) into a commercially available least 50 mole W ethylfine Sald group pf having emulsion described herein and sold under the trade name a reduced specific l p of at least 1 dqclhter/g' of Poly 500 sfiries by Spencer Chemical ca Which golymer and containing 0.1 to 3.0 milhequlvalents carhad been diluted to 12.5 weight percent solids with dis- Per i tilled water. The swatch was wrung out through rubber 4 The arthcle accordmg to clam 1 Wherem the squeeze rolls. After redipping and rewringing the swatch, 1S a cqpolymer of ethylene. and.m?thacryhc it was clamped between two picture type frames having and whefem a pomqn of the methacryh? field 18 present 10" X 10" squares cut from their centers. The clamped Soqmm salt said copolymer contammg swatch was baked in a forced air oven for 10 minutes at g %g i gf Per i i h 1 150 C. The dried swatch was then removed from the e at h accor i to c alm w erein 6 Po frames and rev/sighed. The Weight Percent adcLon iamer member 1s a modified polyethylene with attached difference in weight between the emulsion treated swatch F'i i the a s; the group and the relaxed swatch, was 11.3%. The area of the 2 33 a y gi g i h I swatch within the markings was remeasured and desigaccorhmlg 0 c I erem 6 pc i" nated as the initial area. The swatch was then subjected 5 3 i i i z i gfizgig g gg ymer m to 10 washing and drying cycles with measurements to 5 The article ac'cordin to claim 1 wherein 01 ascertain percent shrink being taken after the tenth cycle. member is an oxidizgd o1 eth lene P Y The washing cycle consisted of washing the swatch in a P y y 3 lb. load with 30 g. of a detergent under the trade name References Cited Tide sold by Procter & Gamble Co. and water at 85-96 C. in a Sears Roebuck automatic washer (Model UNITED STATES PATENTS No. 110-59156'10) delicate fabric setting having a sudsing 2,496,989 2/1950 P Y 161 X time of 4 minutes in the complete 17 minute washing 2,592,526 4/ 1952 Seedcycle. The swatch was then dried in 9, Sears Roebuck 2,653,919 9/1953 H ter 117-16'1 X gas dryer (Model 6107502) for 18 minutes (hot setting) 2,678,286 5/1954 Brunet et -1 1 at an air temperature of about 84 C. at the dryer exg 28 Embed et haust. The marked area on the swatch had a 1.5% shrink J ChaPPJaH after the tenth cycle. The hand of the thus washed swatch Hardmg 117*141 X was not efiected by the herein described treatment. A 65 WILLIAM D, MARTIN, Primary Examiner.

control wool swatch 12" x 12" with a 10" x 10" marked area which had been relaxed as above but not treated with the emulsion showed a 25.0% shrink after the tenth cycle.

H. J. GWINNELL, Assistant Examiner.

US .Cl. X.R. 1l716'1; 8-18, 54 

